Chromiferous dyestuff and process of making same



Patented Jan. 29, 1935 ,cHRoMIFERoUs DYESTUFF AND PROCESS OF MAKING SAME Fritz Straub, Basel, and Hermann Schneider, I Riehen, near Basel, Switzerland, assignors to the firm of Society of Chemical Industry in Basie, Basel, Switzerland N Drawing. Application March 29, 1934, se ial -No. 718,081. In SwitzerlandAprilB, 1933 10 Claims.

It has been found that chromiferous dyestuffs are obtained from azo-dyestuffs of the general formula wherein R1 and R2 represent naphthalene radicals and n means the number 1-2, wherein further the two hydroxyl-groups stand in orthoposition to the azo bridge, and the hydroxylgroup of the naphthalene radical R2 stands in the 2-position of the'naphthalene radical, by treating these azo-dyestufis with such complex ,7, compounds which are produced by the action of organic compounds containing at least one hydroxyl-group on alkaline suspensions of chromium hydroxide.

For making the parent azo-dyestuffs there may be used, for example, diazotized l-amino-Z-hydroxynaphthalene-i-sulfonic acid, diazotized 2- amino 1 hydroxynaphthalene- 4 sulfonic acid diazotize'd 1 amino 2 hydroxynaphthalene 4,8- disulfonic acid, diazotized 1-amino-2-hydroxyg5 naphthalene-4,6-disulfonic acid, diazotized chloroor bromo-1-amino-2-hydroxynaphthalene-4- sulfonic acid, or nitrated 1-diazo-2-hydroxynaphthalene-i-sulfonic acid as the one component and Z-hydroxynaphthalene or a substitution product thereof, such' as chloro-, brorno-, methyl-, orv alko'xy-2-hydroxynaphthalene as the other component.

The treatment of the azo-dyestufi with such .complex compounds which are produced by the 5 action of organic compounds containing at least one hydroxyl-group on alkaline suspensions of chromium hydroxide, as for instance a polyvalent alcohol or phenollfor example glycerin, glycol, gallic acid)., a tanning material such as, for

0 example, tannin, a sugar, a cellulose derivative (for example sulfitewaste liquor) 'or a lignin, may consist for. instance in heating together in an open vessel or under pressure a chromium salt, anexcess of alkali (for instance caustic soda solution or caustic potash solution), the organic compound containing at least one hydroxylgroup and the azo-dyestufi, or in heating the azo-dyestuffs with such complex compounds which are produced by the action of'organic com- .79 pounds containing at least one hydroxyl-group on alkaline suspensions of chromium hydroxide, the operations being conducted in the presence or absence of a suitable further substance, such as a soluble inorganic or organic salt or the like.

The proportion of the azo-dyestufi to the alkaline chroming agent, as well as the proportion of the alkaline chroming agent to the organic compound containing at least one hydroxyl gr'oup may vary within wide limits. Moreover, the duration of the treatment as well as the concentration of the alkali may be varied in many. Ways.

The chromiferous dyestuffs obtainable by this process dye animal fibres, such as for'exam'pl'e,

wool and silk, navy-blue to black tints, both ma sulfuric acid bath and, particularly advantageously, in the manner described in theU. S. Patent No. 1,903,884 or'when dyeing in dye-baths containing an aromatic acid besides an inorganic acid. The invention is particularly suitable for making very valuable chrom iferous dyestuffs dye ing navy blue from an ,ortho-hydroxy aminonaphthalene sulfonic acidwhich contains no nitro-group and a 2-hydroxynaphthalene. These chromiferous dyestufis, as compared with those hitherto known and those of this group which dye animal fibres in similar tints, arelevel in dyeing deep tintsand are fastin everyrespect, particularly to rubbing. The invention provides a method of converting the very cheap blue dyestuffs known as fast chrome cyanines into cheap and fast chromium compounds dyeing navy blue, which was not possible by the chroming methods hithertoknown and applied to this group of dyestuffs.

The following examples illustrate the invention the parts being by weight:-

Example '1 I Into a glycerine chromite solution made from 25.6 parts of CI2O3 in the form of a chromium hydroxide paste of 11.5 per cent. strength, 120 parts of caustic alkali of 90 per. cent. strength and 43 parts of glycerine of 90 per cent. strength,and

cooled to 40-50 0., there are stirred 208 parts of the azo-dyestufi of the formula OH HO SOaNa from diazotized 1-amino-2-hydroxynapthalenei-sulfonic acid and mono-sodium 2-hydroxynaphthalenain the form of a paste of about 30 per cent. strength. The mixture is first heated gradually, while stirring, to '7-5-80 C., then kept atthis temperature for 3'hours and then heated for 6-8 hours at 80-85 C. After dilution with water to 300'0'parts, the liquor is neutralized with hydrochloric acid of 10 per cent. strength, while stirring well, then made feebly acid to litmus with formic acid and, after filtration from a small quantity of impurities, evaporated to dryness in-a vacuum. I

The chromed dyestuif obtained dyes wool in a bath acid with organic acid and sulfuric acid navy blue tints of excellent fastness and of good-- color by artificial light. H

Example 2 1-amino-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene' (mono-sodium salt) and the mixture is stirred for 2 hours at C. and then heated for 83hours at 85-90 C.

The blue mixture thus obtained is then diluted with cold water to make about 500 parts, carefully neutralized with hydrochloric acid of 10 per cent. strength, acidified with 5 parts of 1 formic acid, filtered from excess of chromiumand the chromiferous dyestuff salted out.

Itdissolves in water very freely to a blackishblue, solution. It dyes wool a bath acid with organic acid and sulfuric acid navy blue tints of very good fastness.

Exa p e 3 '675 parts of a, paste of the azo-dyestuff from diazotized l-amino- 2-hydroxynaphthalene-4-sulfonic acid and Z-hydroxynaphthalene containing 138.6 parts of the dyestuff, are stirred with 50 parts of caustic soda solution of 30 per cent. strength. In the meantime there is prepared a chromite solution in the following manner:-

Into a mixture of 42 parts of potassium hydroxide of percent. strength and 90 parts of caustic soda solution of 30 per cent. strength there is stirred a chromium hydroxide paste of 12 per 'cent. strengthcontaining 19 parts of @203 and the whole is heated to 60-70 C. to form a1solution. There are then added 35 parts of sulfite cellulose liquor and the mass is poured, while stirring, into the dyestufi solution. After addition of 46 parts of crystallized sodium acetate this mixture is heated, while stirring, first for about 3 hours at 75-80 C. and then for 3 hours at 90-100 C. The black-blue solution produced is then diluted with an equal volume of water, neutralized with mineral acid of 5-10 per cent.

strength and, after filtration from a small quantity of impurities, evaporated to dryness in a vacuum. The new chromium compound is a blue-grey powder, soluble inwater to a blue solution having red dichroism; it .is also soluble to a blue solution in sodium carbonate solution of 10 per cent. strength and sparingly soluble in caustic soda solution of 10 per cent. strength.

Example 4 Into a freshly prepared potassium chromite solution; obtained by stirring a mixture of 70 parts of a chromium hydroxide paste of 8 per cent. strength, corresponding with 5.6 parts Cr2O3, 13 parts of gallic acid and 48 parts of caustic potash of 90 per cent. strength there are introduced 41 parts of the azo-dyestuif from diazotized 1-amino 2-hydroxynaphthalene-4,-sulfonic. acid and 2-hydroxynaphthalene in the form of a paste of 20 per cent. strength. The mixture is heated, while stirring, for 6 hours at 8090 C. and then heated for a further 2 hours at 90-100 C. It is .then diluted with cold water-to 500 parts by volume, neutralized with strongly diluted hydrochloric acid and evaporated to dryness in a vacuum.. The new chromiferous dyestufi is a violet-black powder, soluble in water to a violet blue solution having'strongly red dichroism. In sodium carbonate solution of 10 per cent. strength and caustic soda solution of 10 per cent. strength it dissolves to'a blue-violet solution in each case and in concentrated sulfuric acid to a blackishblue solution. It dyes wool in a bath acid with an organic acid and sulfuric acid navy blue tints of very good properties of fastness.

Emample 5 A potassium chromite solution made by stirring 44 parts of caustic potash of 90 per cent. strength with 6''! parts of a chromium hydroxide paste of 8 per cent. strength, corresponding with 5.4 parts of C1203, is mixed with 20 parts of sulfite cellulose liquor and there are introduced, while stirring, 41.6 parts of the azo-dyestuff from diazotized 1-amino-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene in the form of a paste of 20 per cent. strength; the mixture is heated for 6 hours at 80-90 C. and then for 2 hours at 90-100 C. It is then diluted with 300 parts of water, filtered from a small quantity of insoluble matter, neutralized with strongly diluted hydrochloric acid and mixed with common salt to salt outthe chromiferous dyestuff. The latter when dry is a violet-black powder, soluble in water to a blue, strongly dichroic solution. In sodium, carbonate solution of 10 per cent. strength, caustic soda solution of 10 per cent. strength and concentrated sulfuric acid it dissolves to a blue solution in eachcase. It dyes wool in a bath acid with organic acid and sulfuric acid navy blue tints of excellent properties of fastness.

' Emample 6.

11.2 parts of the azo-dyestuff'from the chlorinated diazo-compound' of 1'-amin'o-2-hydroxynaphthalene-4-sulfonic acid andZ-hydroxynaphthalene are introduced into a potassium chromite solution which has been freshly prepared from 18 parts of a chromium hydroxide paste of 8 per cent. strength, corresponding with 1.44 parts of C12O3, 11 parts of caustic potash of 90per cent. strength and 3 parts of sugar. After heating the mass, while stirring, first for 6 hours at 80- 90 C. and then for 2 hours at 90-100 C. it is diluted to parts with cold water and the new 'chromiferous dyestuif is precipitated by neutral- Example 7 A chromite solution is prepared from 16.5 parts of a chromium hydroxide paste of 8 per cent strength, corresponding with 1.33 parts of ClzOs. 27 parts of caustic soda solution of 30 per cent. strength and 2 parts of glycerine; into this chromite solution there are introduced 12.4 partsof theaz'o-dyestuff of the formula --on HO SOsH hours at 80-90" C., and then for 2 hours at 90-- 100 C. The new chromiferous dyestuff is precipitated by neutralizing the mass with strongly diluted sulfuric acid. When dry it is a grey-black powder, whichdissolves in water to a blue solution. In sodium carbonate solution of per cent. strength it is insoluble, while in caustic soda solution of 10 per cent. strength it dissolves in traces toa violet solution. In concentrated sulfuric acid it dissolves to a blue solution having red dichroism- It dyes wool in a bath acid with organic acid and sulfuric acid fast navy blue tints.

Example 8 Into a potassium chromite solution containing 104- parts of a'chromium hydroxide paste of 8 per vcent. strength, corresponding with 8.32 parts of --Crz03, parts of caustic potash of 90 per cent. strength and 10 parts of sugar there are introduced 52 parts of the azo-dyestuff of the formula Hols on l SOsH from diazotized 2-amino-l-hydroxynaphthalene- 4:8-disulfonic acid and 2-hydroxynaphthalene. The mixture is diluted with 30 parts of water and heated. while stirring for 6 hours at -90" C. and for a further 2 hours at -100 C. It is dilutcd with 200 parts of cold water, neutralized with strongly diluted mineral acid and evaporated to dryness in a vacuum. There is obtained a --chromiferous dyestufi in the form of a violet black powder which dissolves in water freely to a blue solution having red dichroism. Sodium carbonate solution of 10 per cent. strength dissolves it to a reddish-blue solution with strong red dichroism, while the solution in caustic soda solution of 10 per cent. is violet. Concentrated sulfuric acid dissolves the dyestuff to a blackish blue solution. The dyestuff dyes Wool in a bath acid with organic acid and sulfuric acid navy blue tints of excellent properties of fastness.

Example 9 20.8 parts of the azo-dyestuff of the formula from dia zotized 2-amino-l-hydroxynaphthalene- -sulfonic acid and Z-hydroxynaphthalene are intr'oduced'into a freshly prepared sodium chromite soda solution of 30 per cent. strength and '7 parts of glycerine of 90 per cent. strength. The mixture is stirred and heated for 6 hours at 80-90 C. and then for 2 hours at 90-100 C.; it is then diluted with cold water to 300 parts and neutralized with strongly diluted sulfuric acid. The

chromiferous dyestuff is now salted out. When dry it is a grey-violet powder which'dissolves in water and sodium carbonate solution-of 10 per cent. strength to a red-violet, strongly red di- I chroic solution; in caustic soda solution of 10' per cent. strength it dissolves to a violet. solution and in concentrated sulfuric acid to a blackish bluegreen'solution. It dyes. wool in a bath acidwith organic acid and sulfuric acid excellently fast I navy blue tints with a reddish tone.

' Example 10 46.1 parts of the azo-dyestuff of the formula from the nitrated diazo-compounol of l-amino-2- hydroxyhaphthalene--sulfonic acid and 2-hydroxynaphthalene are stirredinto a sodium chromite solution, which has been freshly made from Z 70 parts of a chromium hydroxide paste of 8 per cent. strength, corresponding with 5.7 partsof ClzOa, parts of caustic soda solution of 30 per cent. and ZOparts of sugar. The mixture is diluted with parts of water and stirred and heated for 6 hours at '75 8 0 C. and then for 3 hours at 80-90 C. The mass is introduced into 1500 parts of .hot'water, made strongly acid to litmus paper with slightly diluted formic acid,

filtered from insoluble matter and the filtrate 5i evaporated to dryness. The chromiferous dyestuff is a black powder, soluble in water to a brown violet-black solution. In sodium carbonate solutionof 10 per-cent. strength and caustic soda solution of 10 per cent. strength itis dissolved only in traces to solutions of the same color,

whereas in concentrated sulfuric acid it dissolves to a blackish-blue solution. The dyestufi' dyes wool in a bath acid with organic acid and sulfastness.

What we claim is:- 1. Process for the manufacture ofchromiferfuric acid black shades of good properties of l ous dyestuffs from azo-dyestufisbf the general I formula e R1--N=NRz organic compounds containing at least one alcoholic hydi'OXyl-group on alkaline suspensions of chromium hydroxide.

2. Process for the manufacture of-chromiferous dyestuffs from azo-dyestufis of the general formula wherein R1 represents a naphthalene radical and n means the number 1-2, wherein further the hydroxyl-group of the radical R1 stands in orthoposition to the azo-bridge, consisting in reacting these azo-dyestuifs with such complex com-' pounds which are produced by the action of organic compounds containing at least one alcoholic hydroxyl-group on alkaline suspensions of chromium hydroxide.

3. Process for. the manufacture of chromiferous dyestuffs from azo-dyestuifs of the general formula wherein R1 represents a naphthalene radical and the hydroxyl-group of the naphthalene radical R1 stands in ortho-position to the azo-bridge, consisting in reacting these azo-dyestuffs with such complex compounds which are produced by the action of organic compounds containing at least one alcoholic hydroxyl-group on alkaline suspensions of chromium hydroxide.

4. Process for the manufacture of chromiferous dyestuffs from theazo-dyestuif of the formula SOsH consisting in reacting this azo-dyestuif with such complex compounds which are produced by the action of organic compounds containing at least one alcoholic hydroxyl-group on alkalinesuspensions of chromium hydroxide.

5 Process for the manufacture of a chromiferous dyestuff from the azo-dyestuff of the formula SOaH consisting in reacting this azo-dyestuff with such complex compounds which are produced by the action of glycerine on suspensions of chromium hydroxide.

6. Chromiferous dyestuffs, obtained from the azo-dyestufis of the general formula wherein R1 and R2 represent naphthalene radicals and n means the number 12, wherein further the two hydroxyl-groups stand in ortho- 'position. to the azo-bridge,--and the hydroxylgroup of the naphthalene radical R2 stands in the 2-position of the naphthalene radical, by reacting these azo-dyestuifs with such complex compounds which are produced by the action of organic compounds containing at least one alcoholic hydroxyl-group on alkaline suspensions of chromium hydroxide, which products represent grey and black powders, dissolving in water to violet, blue and black solutions, and dyeing wool blue and black tints of very good fastness properties,

7. Chromiferous dyestuffs, obtained from the azo dyestuifs of the general formula IE{I -N=ITI soaiEi)u wherein R1 represents a naphthalene radical and n means the number 1-2, wherein further the hydroxyl-group of the radical R1 stands in orthoposition to the azo-bridge, by reacting these azodyestuffs with such complex compounds which are produced by the action of organic compounds containing at least one alcoholic hydroxyl-group on alkaline suspensions of chromium hydroxide, which products represent grey and. black powders, dissolving in water to violet, blue and black solutions, and dyeing wool blue and black tints of very good fastness properties.

8. Chromiferous dyestuffs, obtained from the azo-dyestuifs of the general formula wherein R1 represents a naphthalene radical and the hydroxyl-group of the napthalene radical R1 stands in ortho-position to the azo-bridge, by reacting these azo-dyestuifs with such complex compounds which are produced by the action of organic compounds containing at least one alcoholic hydroxyl-group on alkaline suspensions of chromium hydroxide, which products represent grey and black powders, dissolving in water to violet, blue and black solutions, and dyeing wool blue and black tints of very good fastness properties.

9. Chromiferous dyestuffs, obtained from the azo-dyestuif of the formula 10. The chromiferous dyestufi, obtained from the azo-dyestufi of the formula III N OH HO 10 by reacting this azo-dyestufi with such complex compounds which are produced by the action of glycerine on suspensions of chromium hydroxide, which product represents a grey to black powder dissolving in water to a violet to blue solution, and dyeing Wool navy blue tints of very good fastness properties and excellent appearance in the artificial light. 

